US3281392A - Polyoxymethylene compositions stabilized with pyrimidine derivatives - Google Patents

Polyoxymethylene compositions stabilized with pyrimidine derivatives Download PDF

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Publication number
US3281392A
US3281392A US286185A US28618563A US3281392A US 3281392 A US3281392 A US 3281392A US 286185 A US286185 A US 286185A US 28618563 A US28618563 A US 28618563A US 3281392 A US3281392 A US 3281392A
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polyoxymethylene
polymer
weight
group
polymeric composition
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US286185A
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Oddo Nino
Porra Angelo
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Montedison SpA
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Montedison SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings

Definitions

  • This invention is directed to a thermally stable composition and more specifically to a thermally stabilized poyoxymethylene composition. Still more specifically, this invention is directed to the stabilization of polyoxymethylenes against high temperatures with pyrimidine derivatives.
  • polyoxymethylenes are characterized by a high thermal degradability and that at their melting point or at a higher temperature, they will depolymerize.
  • the depolymerization of the polyoxymethylene chain may take place by at least three different mechanisms:
  • organic compounds are being used as stabilizers, each being a specific inhibitor for one of the possible degradation processes such as peroxidation or splitting of the chain through a different chemical mechanism.
  • stabilizing agents or inhibitors include such organic compounds as the aromatic amines, phenols, and other known antioxidants. These antioxidants may also be used with other stabilizers capable of blocking the depolymerization mechanisms and include such known compounds as the polyamides, polyurethanes, urea, etc.
  • a stabilizer comprising a pyrimidine derivative.
  • the pyrimidine derivatives to be used for purposes of this invention are selected from the group consisting of derivatives of barbituric acid and uric acid. More specifically, these derivatives can be represented by the general Formulae I and II, respectively.
  • the preferred compounds include those wherein R and R is either a hydrogen atom or an alkyl, isoalkyl or aryl group and X is either an oxygen or sulfur atom.
  • Typical examples which come within the Formula I include 5-phenyl-5-ethyl barbituric acid, 5,5-diethyl barbituric acid, 5-ethyl-5-(l-methyl-butyl) barbituric acid, 5-ethyl-5-(l-methyl-butyl)2-thiobarbituric acid, 5-allyl-5- diphenyl barbituric acid, 5,5-diphenyl barbituric acid, 5- ethyLS-isoamyl barbituric acid, 5-allyl-5-(l-methylbutyl) barbituric acid, S-VinyI-S-n-butyl barbituric acid, S-ethyl-S- cyclohexyl barbituric acid, S-phenyl barbituric acid, 5- ethyl-Z-thiobarbituric acid, and 5,5-diethyI-Z-thiobarbituric acid.
  • Typical derivatives which are represented by the general formula II include compounds wherein R, R and R" are either a hydrogen atom or an akyl, isoalkyl or aryl group, and X and Y are either an oxygen or sulfur atom.
  • R, R and R" are either a hydrogen atom or an akyl, isoalkyl or aryl group, and X and Y are either an oxygen or sulfur atom.
  • Typical derivatives which are represented by the general formula II include compounds wherein R, R and R" are either a hydrogen atom or an akyl, isoalkyl or aryl group, and X and Y are either an oxygen or sulfur atom.
  • Examples of these compounds include the methylxanthines such as theobromine, theophylline, caffeine, etc.
  • the thermal stability of the polyoxymethylenes can be materially improved by the addition of a small but an efiective amount of a well-known antioxidant in combination with one or more of the above-identified pyrimidine derivatives.
  • a synergistic result can be obtained by using a common antioxidant in combination with the pyrimidine derivative. This was recognized by the fact that the thermal stability of the polyoxymethylene polymers 'was substantially higher when a combination of the antioxidant and pyrimidine derivative was used in comparison to the use of either one of these compounds alone.
  • the antioxidants do not by themselves protect the polyoxymethylene against depolymerization or a lowering of molecular weight at high temperatures. In general, the antioxidants do not prevent the breaking of the acetalic bridges along the polymeric chain which causes a decrease in the in herent viscosity of the product.
  • the polyoxymethylene compositions of this invention are substantially unaltered in their inherent viscosity even after prolonged heat treatments, in the presence of air, at substantially higher temperatures. It was also noticed that the polymers were protected against color change and were maintained perfectly white after long periods of heating in the presence of oxygen.
  • the pyrimidine derivatives may be incorporated into the polymer by any of the known techniques suitable for obtaining a uniform dispersion of a powdered solid in a polymer.
  • the addition may be carried out at room temperature in a powder mixture or at a temperature higher than the melting point of the polymer in a roll mixer or in a screw extruder.
  • Still another technique for preparing the mixture consists of dissolving the pyrimidine derivative in a suitable solvent and subsequently impregnating the polymer with the solution and then drying the mixture.
  • the percentage or concentration of the stabilizing agent of this invention in comparison to other known stabilizers is relatively low.
  • the pyrimidine can be added in amounts ranging up to about 15% by weight of the polymer and can be used in amounts as low as 0.001% by weight.
  • the stabilizing agent may range from about 0.01 to by weight of the polymer.
  • other known additives such as plasticizers, pigments, etc., may be used in combination with the polymer.
  • the thermal degradability or stability of the polyoxymethylene polymers stabilized in accordance with the teachings of this invention was determined by placing approximately 0.1 gram of the polymer in an oven at a temperature of about 200 C. and in the presence of air.
  • the viscosity data was obtained from solutions of the treated polymer in dimethyl formamide at a concentration of about 0.5 gram of polymer per 100 cc. of solvent, at a temperature of about 150 C. and in the presence of 1 gram per 100 cc. of the solvent of diphenyl amine.
  • the results of the test were determined by the inherent viscosity defined as follows:
  • the polyoxymethylene polymers used in the test are characterized by long sequences of (CH O) units which have an inherent viscosity of at least 0.3.
  • the polymer can be obtained by known methods from aqueous CH O solutions or with anhydrous CH O or with trioxane.
  • the polymers stabilized in accordance with this invention are particularly suited to be used for the preparation of films, fibers, molded articles and similar materials which can be obtained by extrusion, injection molding, or other known methods.
  • Example 1 A polyoxymethylene dihydroxide was prepared by the polymerization of anhydrous CH O in an anhydrous hydrocarbon solvent such as toluene and in the presence of an anionic catalyst such as tributyl amine at room temperature. The product was acetylated in the presence of acetic anhydride and a hydrocarbon solvent. Samples of the polyoxymethylene diacetate were mixed with the stabilizing agents listed in Table I. The composition was prepared by mixing the polymer and the stabilizing agent in a mill for about 30 minutes. The inherent viscosity of the polymer before and after the mill treatment was approximately 0.68.
  • the mixture was then subjected in accordance with the 4 above-description to a thermal treatment at a temperature of about 200 C.
  • Example 6 in the above-table, that the polyoxymethylene was stabilized by the addition of 3% by weight of S-et-hyl-S-(l-ethyl butyl) barbituric acid without the addition of an antioxidant.
  • example 5 illustrates the effectiveness of a combination of the barbituric acid and diphenyl amine as a synergistic stabilizing agent for the polymer.
  • Example 2 A polyoxymethylene dihydroxide was prepared and acetylated in the presence of acetic anhydride by the method described in Example 1.
  • the polyoxymethylene diacetate product was treated with the stabilizing agents by mixing the polymer and the stabilizers, with agitation, and then subjecting the treated product to a thermal treatment at 200 C.
  • the inherent viscosity of the polymer was approximately 0.70.
  • T 40 0. 25 Sample plus 1% phenylethylbarbituric acid plus 1.0% DFA 6.0 0. 07 Sample plus 37 henylethylbarbituric acid plus Example 3
  • a sample of polyoxymethylene dihydroxide was obtained by polymerizing CH O in an aqueous medium in the presence of some preformed polymer as the solid phase. The method of synthesizing the product is further described in U.S. patent application Serial No. 168,- 220 filed on January 23, 1962. The method consists essentially of contacting an aqueous solution at a temperature of 20 C.
  • the polyoxymethylene product was dried and acetylated in the same manner as described in Example 1.
  • the polyoxymethylene product was dried and acetylated in the same manner as described in Example 1.
  • polyoxymethylene diacetate thus obtained was then treated with a solution of 5-ethyl-5(1-methylbutyl) barbituric acid in ethanol.
  • the amount of barbituric acid in the alcohol was approximately 3% by weight of the polymer.
  • the alcohol was then evaporated by keeping the same at a temperature of about 65 C. under a vacuum for about 4 hours.
  • the treated polymer had an inherent viscosity of about 0.6.
  • the polymer was subsequently thermally treated at a temperature of 200 C. with the results reported in Table III.
  • Example 4 TABLE IV Inherent K'zuo, ViSCOSitY percent after 30 wt. loss min. at 200 C.
  • a thermally stable polymeric composition consisting essentially of a high molecular weight polyoxymethylene containing recurring CH O- units and approximately 0.01 to by weight of the polyoxymethylene of a pyrimidine derivative selected from the group consisting of compounds having the general formula:
  • R and R are selected from the group consisting of a hydrogen atom, alkyl radicals, isoalkyl radicals, and aryl radicals, and X is either an oxygen atom or a sulfur atom and the general formula:
  • R, R and R" are selected from the group consisting of a hydrogen atom, alkyl radicals, isoalkyl radicals and aryl radicals and X and Y are either an oxygen atom or a sulfur atom.
  • composition contains 0.01 to 5.0% by weight of an antioxidant selected from the group consisting of diphenyl amine and 4,4 butylidene bis (6-tert. buty1-3-methylphenol).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
US286185A 1962-06-08 1963-06-07 Polyoxymethylene compositions stabilized with pyrimidine derivatives Expired - Lifetime US3281392A (en)

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IT1159362 1962-06-08

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US (1) US3281392A (en, 2012)
BE (1) BE633388A (en, 2012)
NL (1) NL293709A (en, 2012)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505280A (en) * 1966-12-02 1970-04-07 Hoechst Ag Polyoxymethylene stabilized with mixtures of a ureide acid salt and phenol
US3696170A (en) * 1968-06-04 1972-10-03 Asahi Chemical Ind Stabilized polymer compositions
US4456715A (en) * 1980-07-21 1984-06-26 Bayer Aktiengesellschaft Flameproof polyamide moulding compositions
US20080067710A1 (en) * 2006-09-15 2008-03-20 The Coca-Cola Company Pressurized Tooling for Injection Molding and Method of Using

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505280A (en) * 1966-12-02 1970-04-07 Hoechst Ag Polyoxymethylene stabilized with mixtures of a ureide acid salt and phenol
US3696170A (en) * 1968-06-04 1972-10-03 Asahi Chemical Ind Stabilized polymer compositions
US4456715A (en) * 1980-07-21 1984-06-26 Bayer Aktiengesellschaft Flameproof polyamide moulding compositions
US20080067710A1 (en) * 2006-09-15 2008-03-20 The Coca-Cola Company Pressurized Tooling for Injection Molding and Method of Using
WO2008033767A1 (en) * 2006-09-15 2008-03-20 The Coca-Cola Company Pressurized tooling for injection molding and method of using
US7790077B2 (en) 2006-09-15 2010-09-07 The Coca-Cola Company Pressurized tooling for injection molding and method of using

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BE633388A (en, 2012)

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